Lower alkene polymers

ABSTRACT

This invention describes highly reactive polymers obtained from lower monomers. The polymers are particularly useful in alkylation reactions.

This Application is a divisional application of application Ser. No.07/079,855, filed 7/30/87 now being allowed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process and the resultant compositionwhereby a lower alkene monomer is converted to a lower alkene polymerthrough the use of unique reaction conditions and catalyst system. Thelower alkene polymers so obtained have a high degree ofmono-unsaturation content and are highly reactive in various reactions.

2. Description of the Art Practices

It is known from U.S. Pat. No. 2,816,944 issued Dec. 17, 1957 to Muessiget al that olefinic polymers ranging in a carbon content of from 12 to50 carbon atoms obtained from olefins having 5 to 25 carbon atoms may beprepared by using boron trifluoride with phosphoric acid. It isgenerally disclosed by Muessig et al that the polymerization may takeplace using kieselguhr, and is conveniently conducted at a temperatureof 35° C. to 60° C.

Serniuk in U.S. Pat. No. 2,810,774 issued Oct. 22, 1957 describes anolefin polymerization catalyst system comprising boron trifluoride andacids of phosphorus. It is also disclosed by Serniuk that variousabsorbents such as aluminum silicates, kieselguhr, Fuller's earth, claysand silica gel may be employed as a support system for the catalyst. TheSerniuk reference describes reaction temperatures of 77° F. (24° C.) to212° F. (100° C.) during the polymerization. The olefins of Serniukinclude a mixed propylene-butylene system having an active content ofabout 40% olefins.

U.S. Pat. No. 2,976,338 issued Mar. 21, 1961 to Thomas discloses acatalyst system comprising boron trifluoride and phosphoric acid asbeing too active for polymerizing olefins because of the rapid evolutionof heat. It is disclosed that the boron trifluoride of Thomas may bemodified through the inclusion of a potassium acid fluoride salt to givean acceptable product. The olefins employed by Thomas include from 5 to15 carbon olefins for use in obtaining polymers containing from 10 to 30carbon atoms. The reaction temperatures of the Thomas patent aregenerally in range of 32° F. (0° C.) to 212° F. (100° C.), preferablyfrom 100° F. (38° C.) to 160° F. (71° C.).

It is known from the U.S. Pat. No. 2,416,106 issued Feb. 18, 1947 toLinn et al that olefins may be polymerized through the combination ofboron fluoride and an acid fluoride metal. U.S. Pat. No. 2,585,867 toSparks et al issued Feb. 12, 1952 describes the production of highmolecular weight polymers from monomers using a boron trifluoridecatalyst system with reaction temperatures from -40° C. to -103° C. Inparticular, Sparks is concerned with the reaction of mono-olefins withdi-olefins.

Blewett in U.S. Pat. No. 4,469,910 issued Sept. 4, 1984 describes aprocess whereby a dimer fraction is reacted in an oligomerizationprocess with an alpha-olefin in the presence of a phosphoric acid-modified boron tri-fluoride catalyst system. The Blewett reference isparticularly concerned with the use of 6 to 12 carbon dimers obtainedfrom the monomer which corresponds to the alpha-olefin. Theoligomerization is conducted at from 5° C. to 75° C. U.S. Pat. No.3,985,822 issued Oct. 12, 1976 to Watson describes the production ofpoly-n-butenes using aluminum chloride as a catalyst and employing areaction temperature of 65° F. (18° C.) to 115° F. (46° C.).

U.S. Pat. No. 4,407,731 to Imai issued Oct. 4, 1983 describes catalyticcompositions, useful in oligomerization and alkylation reactions,prepared by treating a metal oxide support such as aluminum with anaqueous solution of an acid. One of the catalysts suggested for use inthe support system of Imai is boron fluoride. U.S. Pat. No. 4,429,177 toMorganson et al issued Jan. 31, 1984 describes obtaining an alpha-olefinpolymer in the presence of a 3 component catalyst system comprising asolid absorbant, boron trifluoride and elemental oxygen. U.S. Pat. No.1,885,060 issued Oct. 25, 1932 to Hofmann et al describes using boronfluoride as a catalyst for propylene or butylene. It is also disclosedthat various hydrogen halides may also be utilized with the boronfluoride.

Schmurling et al U.S. Pat. No. 2,369,691 issued Feb. 20, 1945 describesthe use of sulfuric acid and metal halides of the Friedel-Crafts type.The catalyst system is stated to be useful in the isomerization ofsaturated hydrocarbons, the alkylation of cyclic aliphatic hydrocarbons,and in the polymerization of unsaturated hydrocarbons. U.S. Pat. No.2,404,788 issued Jul. 30, 1946 to Burk et al discloses various aluminateor silicate support systems for boron trifluoride.

U.S. Pat. No. 4,400,565 issued to Darden et al Aug. 23, 1983 describesoligomerizing olefins in the presence of boron trifluoride and aco-catalyst comprising a heterogeneous cationic ion exchange resin. U.S.Pat. No. 2,442,645 to Elwell et al issued Jun. 1, 1948 describes thepolymerization of normal lower mono-olefins which are dissolved inliquid sulfur dioxide. The reaction according to Elwell is carried outin the presence of a boron fluoride catalyst.

U.S. Pat. No. 2,406,869 to Upham issued Sept. 3, 1946 describes thepreparation of an olefin polymerization catalyst comprising borontrifluoride and a hydrogen halide source. U.S. Pat. No. 2,199,180 toLaughlin which issued Apr. 30, 1940 describes the use of sulfuric acidand phosphoric acid for the polymerization of lower olefins. It isstated in Laughlin that it is desirable when treating the lower olefinsto maintain the reaction temperature of above 200° F. (95° C.).

U.S. Pat. No. 2,536,841 issued Jan. 2, 1951 to Dornie describes the useof aluminum halides to polymerize olefins. The reaction temperaturessuggested by Dornie are from 0° C. to -164° C. Dornie utilizes alow-freezing non-reacting solvent such as chloroform or sulfur dioxidein his process. U.S. Pat. No. 2,357,926 issued Sept. 12, 1944 to Bannondescribes the use of boron fluoride and water for the polymerization ofolefins.

U.S. Pat. No. 2,569,383 to Leyonmark et al issued Sept. 25, 1951describes the polymerization of olefins from mono-olefins andpolyolefins to give drying oils. U.S. Pat. No. 2,960,552 to Wasleyissued Nov. 15, 1960 describes the use of methylchloride and borontrifluoride gas to polymerize lower olefins. U.S. Pat. No. 2,855,447issued Oct. 7, 1958 to Griesinger et al describes an example of thepolymerization of lower olefins through the use of hydrogen fluoride andboron trifluoride at temperatures of about 175° F. (79° C.). Block et alin U.S. Pat. No. 3,126,420 issued Mar. 24, 1964 describes the use ofphosphoric acid and kielsguher to polymerize propylene at temperaturesof 450° F. (232° C.) to 650° F. (343° C.). The conditions for Block'sreaction are from 600 to 1200 psi (4,100 KPa -8,100 KPa). Griesinger inU.S. Pat. No. 2,855,447 issued Oct. 7, 1958 discloses that olefins maybe polymerized with boron trifluoride.

Perilstein in U.S. Pat. No. 3,749,560 issued Jul. 31, 1973 describes thepolymerization of a mixture of mono-olefins from C-12 and greaterthrough the use of aluminum trichloride at temperatures of about 15° C.to give polymers having a molecular weight of about 350 to about 1,500.Robert in U.S. Pat. No. 3,932,553 issued Jan. 13, 1976 discusses thepolymerization of propylene in the presence of butadiene at 0° C. to 60°C. with boron trifluoride. Robert further discloses the use ofphosphoric acid catalytic treatment of the di-olefin at from 130° C. to250° C. British patent No. 1,449,840 to Sanders published Sept. 15, 1976describes the alkylation of benzene through the use of a Friedel-Craftscatalyst system.

It has been found in the present invention that a high vinylidenecontent polymer may be obtained by reacting a lower alkene monomer inthe presence of a boron trifluoride and mineral acid catalyst system atabout -3° C. to about -30° C. thereby giving an olefin polymer which isuseful for producing an oil soluble composition. The olefin polymers ofthe present invention are highly reactive materials in that they containa large degree of reactive mono-unsaturation.

Throughout the specification and claims percentages and ratios are byweight, temperatures are in degrees Celsius, and pressures are in KPagauge unless otherwise indicated. Ranges and ratios utilized herein areillustrative and such may be combined to further describe the invention.It is also understood that mixtures of ingredients may be employed foreach stated ingredient. The references cited herein are, to the extentapplicable, incorporated by reference for their disclosures.

SUMMARY OF THE INVENTION

The present invention describes a process for preparing a lower alkenepolymer from a lower alkene monomer feed-stream, including the steps of:(A) contacting the lower alkene monomer with a catalyst systemcomprising boron trifluoride and at least one acid and (B) polymerizingthe lower alkene monomer in the presence of the catalyst system at atemperature of about -3° C. to about -30° C. thereby obtaining a loweralkene polymer having a molecular weight of about 250 to about 500.

A further feature of the invention is a composition of matter which is apolymer of a C₂₋₆ mono-olefin having a molecular weight of about 250,preferably at least about 300, to about 500 and a vinyldiene totrisubstituted olefin content of at least 1:4, typically at least 1:3and more typically at least 3:7 by weight.

Another feature of the invention is a composition of matter which is thepolymer of a C₂₋₆ mono-olefin having the above-described molecularweight and a combined weight ratio of trisubstituted andtetrasubstituted olefin to the vinylidene of less than 9:1, typicallyless than 8:1, more typically less than 6:1 and most typically less than4:1. Alternatively, the vinylidene to tetrasubstituted olefin weightratio is at least 7:11.

Also described herein are various products including the lower alkenepolymer, and the reaction product of the lower alkene polymer with anaromatic compound such as phenol, toluene or benzene and theirsulfonated derivatives. Further described herein are overbasedcompositions of the above sulfonated derivatives. The reaction productsof the lower alkene polymer and a carboxylic acid acylating agent suchas maleic acid or anhydride are also disclosed.

DETAILED DESCRIPTION OF THE INVENTION

The present invention deals with the polymerization of lower alkenemonomers to obtain a lower alkene polymer having a molecular weight ofabout 250, preferably about 300, to about 500. The products obtained inthe invention have a high degree of mono-unsaturation content typicallyat least about 85 mole percent of the polymer, preferably at least about90% and even more preferably 95%-100%.

The polymerization of the lower alkene monomer to the polymer desirablygives a product which contains a high vinylidene content. A vinylidenestructure is as follows:

    (R).sub.2 C═CH.sub.2                                   (A)

where each R group contains at least one carbon atom. As the various Rgroups become more complex, the later described alkylation processbecomes more difficult. Moreover, the presence of a significant amountof trisubstituted olefin (B) or tetrasubstituted olefin (C), as shownbelow, significantly reduces the reactivity in alkylation reactions.

    (R).sub.2 C═CH(R)                                      (B)

    (R).sub.2 C═C(R).sub.2                                 (C)

Thus, internal olefins are not as reactive in alkylation reactions asare vinylidene components.

In the present invention, the vinylidene content may be augmented by anyalpha-olefin content present in the product or added to the product. Analpha-olefin is of the formula:

    RHC═CH.sub.2                                           (D)

For convenience in defining the present invention, the followingcriteria is employed. The vinylidene content of the totalmono-unsaturation present is typically at least about 15%, moretypically 20% and most typically at least 25%. The weight ratio ofvinylidene to trisubstituted olefin is about 1:4 to about 8:1, typicallyabout 1:3 to about 5:1, and often at least 1:4 and more typically atleast 1:3. The amount of vinylidene and other substituted olefins areconveniently obtained by carbon 13 NMR as referred to in Determinationof Molecular Structure of Hydrocarbon Olefins by High Resolution NuclearMagnetic Resonance, Stehling et al, Anal. Chem. 38, (11), pp. 1467-1478(1966). See also ¹³ C Chemical Shifts of Some Model Olefins by Couperuset al, Org. Magn. Reson. 8, pp. 426-431 (1976). The foregoing articlesare incorporated by reference.

In conjunction with the vinylidene content, it is preferred that theunsaturation content of the polymer is as defined as above anddetermined by ASTM D-1159-66 (Reapproved 1970) herein incorporated byreference.

The lower alkene polymer is obtained from a lower alkene monomertypically containing from about 2 to about 6 carbon atoms. Typically,the lower alkene monomer contains from about 2 to 4 carbon atoms such asbutene and most preferably propylene (propene).

The feed stream of the lower alkene monomer is preferably free of dieneor higher moieties. The diene or higher unsaturated moieties can lead tothe formation of diphenyl alkanes upon alkylation. By beingsubstantially free of diene moieties, it is desired that there be nomore than 10%, preferably no more than 5% by weight of diene or higherunsaturated moieties present in the feed stream. Most preferably, it isdesired that the feed stream be completely free of diene moieties.

It is also highly desired that the alkene monomer such as the propyleneor butene be an alpha olefin. By alpha olefin is meant that theunsaturation in the alkene monomer is between the first and secondcarbon atoms in the molecular structure. A further desired feature ofthe present invention is where the lower alkene monomer is at least 95%of a single species. By single species, it is meant that a single loweralkene monomer is the predominant species within the feed stream. Thatis, where the lower alkene monomer contains 4 carbon atoms, it isdesirable that the monomer is substantially pure 1-butene rather than ina mixture with 2-butene or isobutylene. Of course, for the preferredpropene only one isomer, e.g., 1-propene, exists.

The feed streams for the present invention are typically obtainedthrough catalytic cracking of petroleum feed stocks. Thus, all of thelower alkene monomers with which the present invention is concerned areavailable as articles of commerce.

The lower alkene polymer obtained according to the present inventiontypically has a molecular weight between about 250, preferably about300, and about 500, preferably about 325 to about 475, more preferablyfrom about 350 to about 450, and most preferably from about 380 to about420. The lower alkene polymer, as later discussed, is convenientlyutilized for the alkylation of benzene or other aromatic compounds whichare then further converted to form alkylated aromatic sulfonic acidswhich are utilized as detergent substrates for overbasing in thelubricant industry. Other uses, as later described herein, are thealkylation of acylating agents such as carboxylic acids and anhydrides,phenols and the like.

The catalyst system employed herein has as a first component borontrifluoride. The boron trifluoride may be obtained as the gascommercially, generated in situ or obtained as the etherate.

The second component utilized as part of the catalytic system is astrong acid such as a mineral acid. The mineral acids include thehydrogen halides, sulfuric acid, sulfurous acid and the variousphosphoric acids. Among the phosphoric acids are H₃ PO₄, HPO₃ and H₄ P₂O₇. Any strong acid may be employed in the present invention providedthat the desired polymer is obtained. Thus, while phosphoric acid orsulfuric acid are the preferred acids for use herein, any highly proticacid may be used. Thus, strong acid resins such as Amberlyst™ may beused in the present invention. The amount of acid is that amountsufficient to catalyze the reaction typically about 0.005% to about 1%by weight of the polymer.

It is also possible to superacidify the acids employed herein. Thus, itis possible to use oleum (fuming sulfuric acid) or glacial phosphoricacid through the introduction of P₂ O₅ to phosphoric acid in order toincrease the acid strength. It has been found, however, that the typicalcommerical strength acid, e.g., 85% phosphoric or 98% sulfuric areadequate within the present invention to accomplish the desiredpolymerization of the lower alkene monomer to the lower alkene polymer.Typically, a preferred acid is an aqueous solution containing 70-95% byweight of phosphoric acid (H₃ PO₄).

The boron trifluoride is employed such that it saturates the reactionmixture. Due to the strength of both the acid and the corrosive natureof the source of boron trifluoride, it is suggested that the reactionsbe run in a glass lined or stainless steel vessel. Under the conditionswith which the present invention is practiced, it is acceptable to runat atmospheric pressure.

It is believed that the restrictive temperature conditions under whichthe lower alkene monomer is polymerized in the presence of the catalystsystem gives the high degree of unsaturation content retained in thepolymer together with the narrow molecular weight distribution. In thepresent invention, it is highly desired that the product bemono-unsaturated so that it may be alkylated onto an aromatic ring inthe desired manner. The subsequent alkylation conditions are such thatinternal unsaturation in a polymer of similar molecular weight butprepared outside the scope of the present invention will result indegradation of the polymer or products other than the desired alkylationproducts. Thus, temperature is viewed as being critical to the scope ofthe present invention in order to obtain the high vinylidene contentwith the desired 250 to 500 molecular weight. The temperature conditionsunder which the desired products of the present invention are obtainedare from about -3° C. to about -30° C., preferably about -5° C. to about-25° C. and most preferably about -8° C. to about -20° C. It wasunexpected that the narrow temperature ranges within which the reactionis run in order to obtain the lower alkene polymer from the monomerwould also result in a material which had a high reactivemono-unsaturation content of the desired molecular weight.

The catalyst system as previously discussed may be immobilized,heterogeneous, supported or in any other manner in which catalysts areutilized provided that the objects of the invention are met. Thesubstrates which may be employed in the present invention includekieselguhr, clay, charcoal, aluminosilicates, alumina, silica,diatomaceous earth and various other metal silicates.

A heterogeneous catalyst system would, for example, simply be a mixtureof BF₃ (boron trifluoride) and the acid, e.g., phosphoric. Typically,the heterogeneous system is obtained by bubbling gaseous borontrifluoride through the liquid acid/monomer/polymer mixture.

The temperature conditions of the present invention are met through theuse of standard cooling devices. It is preferred that the polymerizationof the lower alkene monomer to the lower alkene polymer be conductedsuch that the temperature of the reactants does not exceed the desiredparameters for any substantial period of time during the processing.Thus, if a batch system is employed in order to obtain the lower alkenepolymer, the reaction vessel and the contents should be maintainedwithin the desired temperature range until substantially no lower alkenemonomer is present, e.g., 5% or less. Where a continuous processingsystem is utilized, the lower alkene polymer is drawn off as it isformed.

Various solvents may be used in the present invention. It isconveniently preferred that a paraffinic hydrocarbon solvent which isnormally liquid be employed herein. The solvents should be materialswhich are easily distillable from the reaction mixture following thepolymerization reaction. Suitable examples of solvents include hexane,pentane, heptane, or butane. Other suitable solvents include halogenatedaliphatics or carbon disulfide.

The following are examples of the present invention.

EXAMPLE I

A mixture is prepared comprising 200 grams hexane, 8 grams of phosphoricacid and 80 grams of DD1600 filter aid. The filter aid is utilized asthe catalyst substrate. The premixture is obtained by first combiningthe filter aid and the hexane and thereafter adding 85% phosphoric acidto the mixture. The mixture is stirred for about 30 seconds.

A 12-liter, 10-necked round bottom flask equipped with a stirrer,thermometer, dry ice/isopropanol condenser, 4 surface inlet tubes forpropylene and 1 surface inlet tube for boron trifluoride is charged withthe material described above. An additional 2200 grams of hexane solventis added to the system.

The mixture described above is cooled to -20° C. and boron triflurorideis introduced to the system at 1.0 cubic foot per hour (1.25 moles/hour)for 20 minutes until the system is saturated. Evidence of saturationwill be observed by boron trifluoride fumes venting from the condenser.The rate of flow of the boron trifluoride is then adjusted to about 0.2cubic foot per hour (0.25 mole/hour). The latter rate of borontrifluoride flow is maintained for the duration of the polymerizationreaction.

Propylene gas is then added through the remaining 4 inlet tubes at 20cubic feet per hour total (25 moles/hour). The temperature bath ismaintained at -46° C. to -60° C. to hold the -20° C. charge temperature.The flow rate of propylene is about 1 drop per minute condensed on a dryice condenser during the propylene addition. A total of 121 cubic feet(150 moles) of propylene total is charged to the reaction vessel.

The propylene and boron trifluoride feed are stopped and the charge isneutralized with 80 grams of caustic soda liquid (50% aqueous). Thecharge is stirred for several hours to ensure neutralization. Theproduct (lower alkene polymer) is filtered through a cake ofapproximately 30 grams of the DD1600 filter aid.

The product is then vacuum stripped in a separate 12-liter, 3-neckedflask at 30 mm Hg (4 KPa) at 100° C. to remove the hexane. A secondstrip at 9 mm Hg (1.2 KPa) at 163° C. to remove the light ends resultsin the desired product in the amount of 5,418 grams.

The process will give near quantitative conversion to the polymer when aclosed system is employed, e.g., the excess propylene is not vented.

EXAMPLE II

A 12-liter, 10-necked round bottom flask is equipped with a stirrer,thermometer, dry ice/isopropanol condenser, 4-surface inlet tubes forpropylene and 1-surface inlet tube for boron trifluoride. The reactionvessel is immersed in a cooling bath and is charged with 2400 grams ofhexane, 120 grams of silica gel and 12 grams of phosphoric acid in thatorder. The foregoing mixture is stirred at high speed for 15 minutes.

The reaction mixture is cooled to -27° C. and boron trifluoride is addedto the system at 1.5 cubic feet per hour (2.25 moles/hour) for a periodof 23 minutes until the system is saturated. The boron trifluoride flowrate is then changed to 0.1 to 0.2 cubic feet per hour for the durationof the polymerization. The foregoing flow rate is sufficient to maintainsaturation within the system.

Propylene is added through the remaining inlet tubes. The initial feedrate is 20 cubic feet per hour (30 moles/hour). In order to maintain thereaction mixture at -20° C., the flow rate of propylene is decreased by20%. The bath temperature is maintained at -48° C. to -50° C. tomaintain the -20° reaction temperature. The reaction is conducted over aperiod of about 5-1/2 hours at a rate of 1 drop of propylene per minutecondensed on the dry ice condenser during the propylene addition. Atotal 98.3 cubic feet (148 moles) of propylene was charged to thereactor during the reaction time.

Following complete addition of the propylene, the boron trifluoride feedis stopped and the reaction mixture is neutralized with 200 grams ofcalcium hydroxide. The reaction mixture is stirred for several hours toensure neutralization and the charge is filtered through 50 grams ofDD1600.

The filtered reaction mixture is then placed in another reaction vesseland vacuum stripped at 100° C. and 72 mm mercury (9.5 Kpa) to remove thehexane. Subsequently, the reaction mixture is raised to 161° C. and avacuum of 24 mm mercury (3.2 KPa) issued to remove 7 grams of light endmaterial leaving a residue of 4,386 grams of the liquid product.

EXAMPLE III

A detergent alkylate is prepared from toluene and the lower alkenepolymer of Example I.

Toluene in the amount of 4517 grams is added to a 12-liter 4-neck flaskequipped with a stirrer, thermometer sub-surface tube and ice condenser.Thirty grams of aluminum chloride catalyst are also added to the flask.

The mixture described above is saturated with hydrogen chloride gasblowing through the sub-surface tube at 1 cubic foot (1.5 moles) perhour for 0.3 hours. The mixture at this point is cooled to -5° C.

The sub-surface tube is then replaced by an addition funnel and chargedwith 3000 grams of the polypropylene of Example I over a period of 1hour. The reaction is exothermic and is maintained at a temperaturebetween 0° C. and 8° C. Following the complete addition of thepolypropylene the reactants are stirred for an additional 3 hours. Atthis point, 61 grams of ammonium hydroxide are slowly added through anaddition funnel. Following complete addition of the ammonium hydroxide,the mixture is stirred for an additional 0.5 hours.

The reaction mixture is then filtered through 30 grams of DD1600 at 20°C. The filtrate is charged to a 12-liter, 4-necked flask equipped with astirrer, thermometer, goose-neck and condenser receiver flask. Thefiltrate is then vacuum stripped to 160° C. and 10 mm mercury (1.3 Kpa).The product is then allowed to cool to room temperature and filtered asecond time through 30 grams of DD1600 to give 3505 grams of thefiltrate as product.

The yield is approximately 95% wherein the product has an Mn by GPC of402 and a Mw by GPC of 430. The viscosity at 100° C. is 10.79 cks.

A further variation of the use of the composition of the presentinvention is the sulfonation of the above-described detergent alkylateaccording to conventional methods. A still further variation of theabove example is to overbase the sulfonated detergent alkylate. Both ofthe foregoing techniques are known to one skilled in the art.

What is claimed is:
 1. A product by process for preparing a lower alkenepolymer from a lower alkene monomer feedstream, including the steps of:(A) contacting the lower alkene monomer with a catalyst systemcomprising boron trifluoride and at least one acid selected from thegroup consisting of sulfuric acid, sulfurous acid, phosphoric acids, andstrong acid resins and (B) polymerizing the lower alkene monomer in thepresence of the catalyst system at a temperature of about -3° C. toabout -30° C. thereby obtaining a lower alkene polymer having amolecular weight of about 250 to about
 500. 2. The product by process ofclaim 1 wherein the alkene feedstream is substantially free of dienemoieties.
 3. The product by process of claim 1 wherein the lower alkeneis a C₂ -C₆ alkene monomer.
 4. The product by process of claim 1 whereinthe acid is phosphoric acid.
 5. The product by process of claim 1wherein the alkene monomer is an alpha olefin.
 6. The product by processof claim 1 wherein the temperature is about -5° C. to about -25° C. 7.The product by process of claim 1 wherein the alkene is propene.
 8. Theproduct by process of claim 1 wherein the catalyst is supported.
 9. Theproduct by process of claim 1 wherein the acid is an aqueous solutioncontaining 70-95% by weight phosphoric acid.
 10. The product by processof claim 1 wherein the alkene monomer feedstream is at least 95% of asingle species.
 11. The product by process of claim 1 wherein animmobilized catalyst system is employed.
 12. The product by process ofclaim 1 wherein the lower alkene polymer feedstream has an 85% orgreater mono-unsaturation content.
 13. The product by process of claim 1wherein the lower alkene polymer has a molecular weight of about 300 toabout
 450. 14. The product by process of claim 1 wherein the acid issulfuric acid.
 15. The product obtained from the process of claim
 1. 16.The product by process of claim 1 alkylated onto an aromatic ring. 17.The product by process of claim 16 wherein the aromatic ring issulfonated.
 18. The product of claim 1 which is reacted onto a maleicacid or maleic anhydride.
 19. The product by process of claim 17 whereinthe aromatic ring is a phenol.
 20. The product by process of claim 1which is a liquid at 20° C.
 21. The product by process of claim 15having a mono-unsaturation content of 85% or greater.
 22. The product byprocess of claim 1 reacted with an acylating agent.
 23. The product byprocess of claim 17 which is overbased with a metal containing compound.24. A composition of matter comprising a polymer of a C₂₋₆ mono-olefinhaving a molecular weight of about 250 to about 500 and a vinylidene totrisubstituted olefin content of at least 1:4 by weight.
 25. Thecomposition of claim 24 wherein the mono-olefin is propene.
 26. Acomposition of matter which is a polymer of a C₂₋₆ mono-olefin whereinthe polymer has a molecular weight of about 250 to about 500 and acombined weight ratio of trisubstituted olefin and tetrasubstitutedolefin to vinylidene of less than 9:1.
 27. The composition of claim 26wherein the mono-olefin is propene.
 28. The composition of claim 26wherein the weight ratio is less than 17:2.
 29. A composition of matterwhich is a polymer of a C₂₋₆ mono-olefin wherein the polymer has amolecular weight of about 250 to about 500 and a vinylidene totetrasubstituted olefin content of at least 3:7 by weight.
 30. Thecomposition of claim 29 wherein the mono-olefin is propene.
 31. Thecomposition of claim 29 wherein the weight ratio is at least 7:11.